Arylaminoketo compound and preparation



Patented June 13, 1944 ARYLAMINOKETO COMPOUND AND PREPARATION Joseph B. Dickey and James G. McNally, Rochester, N. Y., assignors to Eastman Kpdalg Com-.- pan R h s corp ation O New Jersey Serial No. 409,380

No Drawing. Application September 3, 1941,

7 Claims,

This invention relates to amino compounds containing a substituent having a keto group therein, said substituent being attached to the N of an amino group. More particularly, this invention relates to arylamino compounds con taining an N-d-hydroxy-y-ketoalkyl group in the molecule, as will be described in detail.

This application is a continuation-in-part of our U. S. application SerialNo. 301,466, filed October 6, 1 and is also related in some respects to our applications Serial Nos. 365,108, filed November 9, 1940 (now U. S. Patent 2,323,314, dated July 6, 1943) and 360,626, filed October 10, 1940, (now U. S. Patent 2,336,275, dated December '7, 1943). In our application 301,466 we have described in particular compounds useful in photography, as for example, color photographic developers. The compounds we describe herein are ones useful. in particular as dye intermediates, although certain of the compounds, as will be indicated, may be em,- ployed for photographic purposes, as for example, black-and-white developers, antioxidants, and various other purposes. It is, therefore, apparent that the development, of new compounds which may be employed in a number of Ways industrially is a highlydesirableresult.

This invention has for one object to provide new arylamino compounds having a carbon chain-carbonyl linkage attached to the nitrogen atom of the compound. Still another object is to produce new arylamino compounds of the class indicated, which are useful fer dye. inter? mediates and certain other industrial purposes. A still further object is to produce new compounds of the class indicated wherein the aryl le s may cont in ne 91" mo e su tituen A. sti fu th r o ec i o p vid o e m theds or p pa i h afc d co munes. from various materials. Other objects will appear hereinafter.

We have found that novel amino compounds of the present invention wherein a certain ketccontaining linkage has been introduced in the molecule, imparts to the compound special desirable properties, as for example, properties rendering the compounds particularly usefulqas dye intermediates in the preparation of dyesfor eel-.- lulose acetate fabrics, or compounds for use for certain photographic purposes. Also, certain of our compounds, due to their solubility characteristics and other properties, do not exhibit certain of the undesirable allergenic properties exhib e l y Drier a H PWM Generically our new compounds comprise an a value which will be discussed hereinafter. The

molecule may be substituted in various other respects, as will be discussed, such as for example another atom attached to the nitrogen may be substituted or replaced by various components and, also, the aryl nucleus may have attached thereto various groups,-all of which will be described more fully hereinafter.

Generic formulations illustrating the generic nature of certain of our compounds would be as fol s i In these formulations we have illustrated the most usual example f our compounds wherein the aryl nucleus iscomprised of benzene or naphthalene, which components may be substituted or unsubstituted as exemplified by Z. In many instances, as will be described, we would, for example, employ a compound wherein the aryl nucleus was substituted, as for example, with a lower alkyl group, more specifically exemplified by toluidine.

Our novel compounds of the present invention may be produced by methods comparable to the several methods described in our companion application Serial No. 301,466, above identified. One of these methods may be generically illustrated as follows:

.ing cellulose acetate of the purposesfor which the compounds of our Another method which might be employed is generically illustrated as follows:

B Z (11) R N mesrtyloxxdavmyl \H methyl ketone.etc

i CH1CH -FER invention are useful, it will be observed that, for example, compounds resulting when Z is a hydroxy or amino groups in the ortho or para position are useful for for black-andhite photographic developers.

While the foregoing represents certain of the :generic aspects of our invention, from the numerous compounds thereunder which we, have prepared and tested, there are certain; groups which exhibit special properties and which we may prefer for various reasons. Among these compounds may be listed the-following:

(invent-0H" om-cn -oikons I I oni onz-co-cm oHronoH-oni-on' CHrCHzC O--CH3 photographic purposes such as i halogen, hydroxy, amino, and thionot greater than 5.

CHr-CHiC O-CH;

It will be observed that a number of the foregoing compounds contain a hydroxyalkyl group in the molecule 'and we have found, as will be described in further detail hereinafter, that com- CHr-CHaCO-OH:

' pounds containing the above hydroxyalkyl group and a keto group in the molecule are ones in which we are interested in particular. Further details respecting our invention will be had from a consideration of the following specific ex amples. The first group of examples to be set forth will illustrate a species of compound which may be illustrated by the general formula:

? A on) OR In this formula R represents a member'from the group consisting of alkyl, hydroxyalkyl, alkoxyalkyl, andaryl, R represents a member from the group consisting of alkyl, aryl, and tetrahydrofurfuryl and A is in many instances hydrogen or simple alkyl, but may also be halogen, alkoxyalkyl, amino, or derivatives. thereof. As already indicated, whenA is a hydroxy group in the ortho or para position, the compound has value for use in the 1 photographic field. While we have shown the carbonyl group attached'to a (CH2) 2- group and this is a type of carbon linkage we employ in a number of the examples, as will be observed in another species of compounds to be illustrated, this carbon chain, in addition to being an alkylene chain, may be for example a hydroxyalkyl group. As pointed out above, our preferred compounds will contain a hydroxyalkyl group in the molecule in at least one of the substituents.

Specific compounds and their preparation are set forth in the following examples:

EXAMPLE 1.'y-Ketobutylglycerylaniline 166 gm. glycerylaniline are stirred in water (200 cc.) with '70 gm. methyl vinyl ketone at 50 153 gm. p-methoirYethyl-m anisidine are re acted at in 200 cc. water with gm. ethyl vinyl ketone. The product is extracted with ben-. zene and distilled under reduced pressure. There is obtained a good yield of the desired com: pound boiling. at 190.1195" /1 mm.

EXAMPLE 4. y.-Keto a-methylbutyl-ehydrorcypropylcresidine 200 gm. B-hydroxypropylcresidine are heated ior hours a 4 -1 5 w h 0 sm- .o--pro en 1 cton van t e reac ion pro uct di tilled un r reduced es re- There is btaine a od. d of: t e d s compound boil at 220 2 13' mm.

EXAMPLE 5. 2-glyceryl-'y-ketobutylamino-4-acetamtnoanisole 239 gm. 2-glycerylamino-4-actaminoanisole are reacted with gm. methyl vinyl ketone for 12 hours. The product is recovered by evaporat ing the Water and crystallizing from water.

EXAMPLE 6.-.' -KetobutylgZ2/cerylo-am'sidine 200 gm. glyceryl-o-anisidine are heated in an autoclave (200 cc. water) with 85 gm. methyl vinyl ketone at for 6 hours. On distillation there is obtained a good yield of compound boiling at 195-200/1.5 mm.

140 gm. 5-hydroxyethy1aniline and 110 gm. 'yketobutylbromide are heated in the presence of 100 gm. sodium bicarbonate until no more carbon dioxide is evolved. The product is extracted with benzene and distilled. There is obtained a good yield of the desired compound boiling at ?164/ 1.5 mm.

EXAMPLE 8.' -Ketobutyl-p-hydroa:y propyl-m-amz'nobenzyl alcohol 189 gm. veketobutyl-m-aminobenzyl alcohol are heated in an autoclave at with 60 gm. trimethylene oxide for 8 hours. On distillation there is obtained a good yield of the desired com- R d:

Some of the intermediates that may be prepared using the methods described above are: (1) a-Ethyl-'y-ketoamyl-B-hydroxy 5 ethoxyethyl-m-chloroaniline (2) -Ketobutyltetrahydrofurfuryl-2,5 dimethoxyaniline (3) -Ketobutyl-e-hydroxyethyl-2-methoxy 3 methylaniline (4-) -Ketobutyl-v-methoxy-c hydroxypropylm-ethylbenzene (5) 2-'y-ketobutyl-B-hydroxyethyl-4eacetamino= anisole While the foregoing compounds are satisfactory for producing dye intermediates and are useful for various other purposes, our preferred compounds distinguish therefrom in that not only do they contain a keto group but, also, the substituent containing the keto group also includes a hydroxy group. In other words, the linkage in our preferred compound may be exemplified by:

| H aryl-NQHzC-:C:,R

H o The aryl nuoleus may be benzene, naphthalene, tetrahydroquinoline, benzomorpholine, and the like. R and R have the valuesalready assigned.

These compounds would be prepared by reacting the substituted arylamine with a compound. can.- t m h hvdx xy a bonyl gr i g iscussed. This oqmpoun'd would have one or more reactive atoms to cause its" attachment at the N- position. That is, the reaction producing our preferred compounds might be illustrated somewhat as folllows: r a

is heated in a closed reaction vessel with one mole of methyl aniline at for six hours. When cool the viscous reaction product is removed. This material is pure enough for most uses, but can be purified by distillation under reduced pressure.

One mole of fiehydroxyethylem-toluidine is heated in dioxane at 160-180 with one mole of 'yktobutyi-a, 3-butylene oxide. When cool the product is distilled under reduced pressure.

EXAM LE l s -eild ory-v-krt cmyl cresidine One mole of cresidine is heated as in Example 9 with 2.1 moles 'yrketoamyl-afi-amylene oxide at 180-200 for six to ten hours. 'Ihe product is worked up as previously described.

EXAMPLE 12.,.-N- 3rhydrop:yvy-ketobytyl- O-ch loroam'l ine One mole of O-chloroaniline is reacted as in Example 9, with one mole of 'y-keto-afi-butylene oxide. The reaction product is worked up as in Exam le 5 hilijdrortlethyl -zeethowyfieqcetamino aniline One mole of N-,6ehydroxyezyeketobutylfla ethbxy-S-acetamino aniline is heated in dioxane with 1.1 moles ethylene oxide at 1'70.-..190 for ten hours. The product is' worked up as previously described. V i "Ex supra- 14. N-p-hydroxy- Jcetobutylfl di- 7methyltetrahydroquinoline One mole of 2,7 dimethyltetrahydroquinoline is heated as in Example 9 with one mole oirvketo-a, 8-butylene oxide. The product. is distilled if desired, any unchanged quinoline is removed by steam distillation.

Othercompounds which were prepared by the methods illustrated by the foregoing specific examples, are as follows:

(1) N-p-hydroXy-y-ketobutyl aniline (2) N-B-hydrXy7rlE@l9 uty1 o-toluidine a r (3') N p-hydroxy-v-ketobutyl o-anisidine (4) N-p-hydroxy-v-ketobutyl m-toluidine (5) N-fi-hydroxy-v-ketobutyl-m-anisidine (6) N-fi-h'ydroxy-y-ketobutyl m chloroaniline (7) N-fi-hydroxyl-y-ketobutyl cresidine (8) N-fi-hydroxy'- ,'-ketobutyl 2,5-dialkoxyaniline N-fi-hydroxy-v-ketobutyl roaniline N-e-hydroxy-v-ketobutyl (9) 2-alk0xy-5-chlo- (10) a-naphthylamine (11) N-fi-hydroxy-v-ketobutyl l-amino 5 naphthol v v 12 N-p-hydroxy-v-ketobutyl l-amino -1 .8 e

naphthol (l3) N-p-hydroxy-'y -ketobutyl 2-methylbenzomorpholine (1(1) N-fl-hydroxy-q-ketobtityl 2,5-dimethylbenzomorpholine (1 5) N-B-hydroxy-y-ktobutyl 2,7-dimethylbenzomorpholine (16) N-fi-hydroxy-w-ketobutyl 2-methyltetra hydroquinoline i (17) N-p-hydroxy-y-ketobutyl 2-methyl-7-acetaminotetrahydroquinoline v (18) N-c-hydroxy-v-ketobutyl 2-methyl-7acetaminobenzomorpholine (19) N-B-hydroxy-v-ketobutyl methyl-m-toluir dine I I (20) N-fi-hydroxy-vrketobutyl ethyl-m-toluidine (21) N-fi-hydroxy-ry-ketobutyl N- B-hydroxy- I ethylaniline V 22) N-B-hydroxy-q-ketobutyl N-peth xyethylaniline M v (23) N-p-hydroxy-w-ketobutyl glycerol aniline (24) N-B-'hydroxy-'y-ketobutyl gly'cerol-m-t'oluidine (25) N-p-hydroxy-v-ketobutyl glycerol eresidine (26) N-p-hydroxy'y-ketobutyl butyl cresidine (2'7) N-B-hydroxy-y-ketobutyl butyl-m-toluidine (28). N fi-hydroxy-v-ketobutyl butyl aniline (29) N-p-hydroxy-v-ketobutyl carbityl aniline (30) N-p-hydroxy-v ketobutyl tetrahydrofurfuryl aniline (31) N-e-hydroxy-v-ketobutyl diphenylamine (32) N-fl-hydroxy-v-ketobutyl l-amino 5 naphthol-S-sulphonic acid (33) N-fi-hydroxy-y-vketobutyl oHr-oH- -om 0 l H I Hr--C-CH:

carbons, and the like, various temperatures and solventsmay be employed.

l -(CH2) P -R v H O (0 or p) 0 where A is a group selected from amino, hydroxyl, alkyl, alkoxy, and the like; R is hydrogen,

(snag-( 1 R1 I 0 alkyl, ary1, or heterocyclic; R is an alkyl group; and where y is 1 or 2 and x is zero, 1, or 2.

These compounds may be prepared by a. variety of methods, some of which will be indicated below:

EXAMPLE 15 of sulfuric acid to give a white crystalline sulfate. The compound thus prepared has the formula:

may be prepared.

EXAMPLE 16 In addition to the above compounds some of" the aminophenols which we have found to be of value are listed:

As indicated, the products in accordance with the present invention have many industrial uses, for example, our compounds may be used as dye intermediates in accordance with procedure outlined in our application aforesaid, or as set forth in our Patent No. 2,213,740 dated September 3, 1940. Or certain of the compounds herein described, as exemplified by those wherein the aryl nucleus is substituted in the ortho or para position with a hydroxy group, may be incorporated with various alkalies and other components used in photographic developers to obtain a photographic developer as referred to in our application Ser. No. 301,466.

It is apparent from the foregoing that our invention is susceptible of certain modifications, hence, we do not wish to be restricted excepting insofar as may be necessitated and the spirit of the appended claims.

What we claim and desire to be secured by Letters Patent of the United States is:

1. A compound of the following generah formula: 1

wherein R represents an aryl group of the benzene series, R1 represents a hydroxyalkyl group containing from 2 to 3 carbon atoms, R2 represents an alkylene radical selected from the group consisting of ethylene and methylethylene and R3 represents an alkyl group selected from the group consisting of methyl and ethyl.

2. A compound of the following formula:

cH,-( 3H-0H= 3. A compound of the following formula:

CHT CHIO o-o H:

4. A process for preparing a derivative of an amine comprising heating an aliphatic unsaturated ketone selected from the group consisting of vinyl alkyl ketones and isopropenyl alkyl ketones, with a monooyclic secondary amine of the benzene series.

5. A process for preparing a derivative of an amine comprising heating a vinyl alkyl ketone with a monocyclic secondary amine of the benzene series. 7 r

6. A process for preparing a derivative of an amine comprising heating methyl vinyl ketone with a monocyclic secondary amine of the benzene series.

7. A process for preparing a derivative of an amine comprising heating an aliphatic unsaturated ketone selected from the group consisting of alkyl vinyl ketones and alkyl isopropenyl ketones, with a monocyclic hydroxy alkyl aryl amine of the benzene series.

JOSEPH B; DICKEY. JAMES G. McNALLY. 

